Oleaginous compositions containing phosphorus sulfide derivatives of hexachlorocyclopentadiene-polyolefin adducts



United States Patent f OLEAGINOUS COMPOSITIONS CONTAINING PHOSPHORUSSULFIDE DERIVATIVES 0F HEXACHLOROCYCLOPENTADIENE POLY- OLEFIN ADDUCTSEllis Kirby Fields, Chicago, Ill., assignor to Standard Oil Company,Chicago, 11]., a corporation of Indiana No Drawing. Original applicationJune 26, 1956, Ser. No. 593,792, now Patent No. 2,900,377, dated Aug.18, 1959. Divided and this application Jan. 9, 1959, Ser. No. 785,786

14 Claims. (Cl. 252-'46.7)

g This invention pertains to oleaginous compositions containing novelderivatives of hexachlorocyclopentadiene, and more particularly itrelates to lubricant compositions containing novel compositions ofmatter prepared by reacting a phosphorus sulfide with an adduct ofhexachlorocyclopentadiene with a polyolefin.

This application is a division of my co-pending application Serial No.593,792, filed June 26, 1956, now US. 2,900,377, in which the phosphorussulfide derivatives of hexachlorocyclopentadiene-polyolefin adducts, perse, are claimed.

An object of the present invention is to provide as new compositionsoleaginous compositions containing phosphorusand sulfur-containingderivatives of adducts of hexachlorocyclopentadiene with polyolefins.Another object of this invention is to provide novel phosphorusandsulfur-containing derivatives of adducts of hexachlorocyclopenta-dienewith polyolefins having properties which adapt them for use as additivesfor lubricants. Other objects and advantages of the invention willbecome apparent from the following description thereof.

In accordance with the present invention, the novel composition ofmatter can be prepared by heating the polyolefin withhexachlorocyclopentadiene in mole ratios of 3:1 to 1:1 at temperaturesof from about 85 C. to about 170 C. for a period suflicient to form theadduct, usually for about 2 to 40 hours, removing the unreactedmaterial, and then reacting the resultant adduct with from about 2% toabout 50% of a phosphorus sulfide at a temperature of from about 85 C.to about 200 C. for about 1 to 20 hours. The formation of thehexachlorocyclopentadiene-polyolefin adduct may be conducted atatmospheric pressure or at superatmospheric pressure, for example atpressures up to about 200 pounds per square inch. The reaction of theadduct with the phosphorus sulfide is usually carried out at atmosphericpressure although, if desired, pressures up to about 200 pounds persquare inch can be employed.

The term polyolefin as used herein and in the appended claims meansaliphatic, alicyclic, and aromatic olefins con aining from about 4 toabout 60 carbon atoms and 2 to 6 double bonds. Examples of suchpolyolefins are butadiene, isoprene, l-vinyl cyclohexene-3, dl-limonene(dipentene), myrcene, phellandrene, allo-ocimene, squalene,pheny-l-butadiene, trimethyl-phenyl-allene, 1,6-diphenyl hexatriene,divinyl benzene, etc.

The phosphorus sulfide reacted with the adduct can be P483, P485, P457and preferably P285 01 P4810.

The following examples are given by way of illustrating the presentinvention, and are not intended to limit the same.

EXAMPLE I 83.22 cc. (1 mole) liquid butadiene was allowed to vaporizeinto 160 cc. (1 mole) hexachlorocyc-lopentadiene at 220 F. with stirringand refluxing for about 1.5 hours, and the mixture distilled in vacuo.The resultant adduct 2,963,435 Patented Dec. 6, 1960 2 recovered,amounting to a yield of 70%, had a boiling point of 95 C. at 0.6 mm. anda refractive index (n of 1.5532.

Analysis:

Chlorine, Molecular percent weight Calculated for 0 11501 65. 10 326. 7Found 64. 3325:10

EXAMPLE II EXAMPLE III To 103 cc. (0.65 mole) hexachlorocyclopentadienethere were added slowly over a period of one hour 44 cc. (0.65 mole)isoprcne at a temperature of 230240 F. with stirring. After heating themixture at 300 F. for 0.5 hour, the product was distilled in vacuo,giving a 45% yield of an adduct boiling at 103 C. at 0.5 mm. pressureand an 11 of 1.5519.

Analysis Chlorine, Molecular percent weight Calculated for 010E 61 64.18340. 7 Found 64. 80 350=|=10 EXAMPLE IV A mixture of 68.1 grams (0.2mole) of the product of Example III and 22.2 grams (0.1 mole) P S wasstirred at 280 F.300 F. for 1.75 hours and then filtered hot throughCelite. The filtrate, Weighing 78 grams, was a very viscous brownproduct containing 52.5% chlorine, 4.23% phosphorus and 20.1% sulfur.

EXAMPLE V A mixture of 54 grams (0.5 mole) l-vinyl cyclohexcue-3 and 80cc. (0.5 mole) hexachlorocyclopentadiene was heated to 130 C. At thispoint there was a rapid reaction and the temperature rose sharply to 160C.

The temperature was reduced to 130 C. and maintained there for 6 hours.The product was then distilled, yielding 100 grams of adduct having aboiling range of 159- 167 C. at 0.8 mm. pressure, and an n of 1.5662.

Analysis:

Chlorine, Molecular percent weight;

Calculated for Cal-11101 55. 82 380. 7 Found 54. 371:1:10

EXAMPLE VI A mixture of 19 grams (0.05 mole) of the adduct of Example Vand 5.5 grams (0.025 mole) P 8 was stirred at 340-350 F. for about 15minutes until all of the solid had reacted. Twenty-three grams of a veryviscous brown product was obtained which contained 40.70% chlorine,7.81% sulfur and 3.48% phosphorus.

EXAMPLE VII A mixture of 161 cc. (1 mole) dl-limonene pure) and 80 cc.(0.5 mole) hexachlorocyclopentadiene was heated at 145 C. for 16 hours,and then distilled to a pot temperature of 140 C. at 0.8 mm. pressure.Seventy cc. of dipentene was recovered, leaving a residue of 182 grams.The residue was taken up in 500 cc. hexane, filtered through Attapulgusclay, and evaporated on a steam bath. One hundred twenty-seven grams ofa brown oily product was recovered.

Analysis:

Chlorine, Molecular percent weight Calculated for C HmCl 52.00 408. 7Found 50. 20 415:1:20

EXAMPLE VIII EXAMPLE IX A mixture of 112.5 cc. (0.5 mole based on 75%purity) myrcene and 80 cc. (0.5 mole) hexachlorocyclopentadiene washeated at 230 F. for hours at 300 F. for 4 hours, and the reactionproduct then distilled in vacuo up to a pot temperature of 140 C. at 0.4mm. pres- EXAMPLE X A mixture of 81.7 grams (0.2 mole) of the product ofExample IX and 22.2 grams (0.1 mole) P 8 was stirred at 300 F. for 30minutes at which time all of the solid had reacted. The resultant darkbrown viscous product, amounting to 96.8 grams, contained 39.85%chlorine, 3.99% phosphorus and 9.2 sulfur.

The above described reaction product can be converted to acidicmaterials by steam at a temperature of from about 220 F. to about 400 F.The salt of the acidic products can be obtained by neutralizing the samewith suitable basic reagents such as hydroxides, oxides, sulfides, andcarbonates of an alkali metal, an alkaline earth or a heavy metal, suchas for example NaOH, Nags, K2C03, LIQO, LI2CO3, CaCO CaO, BaO, BaCOBa(OH) SrCO ZnO, PbO, SnO or Cr O Similarly, the acidic products can beneutralized with a basic nitrogen compound, such as ammonia, amines, andthe like.

The herein described phosphorus sulfide derivatives of thehexachlorocyclopentadiene-polyolefin adducts are particularly suitablefor use in amounts of from 0.05% to about 10% as addition agents forlubricating oils to impart extreme pressure properties as well ascorrosion and oxidation inhibiting properties to such lubricants.

Suitable lubricating base oils are hydrocarbon oils, e.g. petroleumoils, synthetic hydrocarbon lubricating oils such as those obtained bythe polymerization of hydrocarbons, and other synthetic lubricating oilssuch as alkylene oxide type oils, for example, the Ucon Oils marketed byCarbide and Carbon Corporation, polycarboxylic acid ester-type oils suchas esters of adipic acid, sebacic acid, azelaic acid, etc. and othersynthetic lubricating oils.

Lubricating oils containing the herein described derivatives exhibitexcellent extreme pressure properties as demonstrated by the data inTable I. TheAlmen values were determined on the Almen Tester in themanner described in the Proceedings of the 15th Annual Meeting AmericanPetroleum Institute, 15, Sect. III, 60 (1934), or the Oil and GasJournal 33, No. 26, 123, 126 (1934).

Table I Concentra Almen Test Product tion Percent b Pass (1b) Fail (lb)Control B Example II Example IV Example VI Example X Example VIII HSolvent-extracted SAE 30 Oil. b Concentration of additive in the controloil.

The eiiectiveness of the herein described derivatives in inhibitingoxidation and the corrosion of copper and/or lead-containing metals,such as, for example, copperlead alloys is demonstrated by subjectinglubricants containing the derivative to the following test.

A copper-lead test specimen is lightly abraided with steel wool, washedwith naphtha, dried and weighed to the nearest milligram. The cleanedcopper-lead test specimen is suspended in a steel beaker, cleaned with ahot trisodium phosphate solution, rinsed with water, acetone and dried,and 250 grams of the oil to be tested, together with 0.625 gram leadoxide and 50 grams of a 30-35 mesh sand charged to the beaker. Thebeaker is then placed in a bath or heating block and heated to atemperature of 300 (:2 F.), while the contents are stirred by means of astirrer rotating at 750 r.p.rn. The contents of the beaker aremaintained at this temperature for twenty-four hours, after which thecopper-lead test specimen is removed, rinsed with naphtha, dried andweighed. The test specimen is then replaced in the beaker and anadditional 0.375 gram of lead oxide added to the test oil. At the end ofan additional twenty-four hours of test operation, the test specimen isagain removed, rinsed and dried as before, and weighed. The testspecimen is again placed in the beaker together with an additional 0.250gram of lead oxide and the test continued for another twenty-four hours(seventy-two hours total). At the conclusion of this time, the testspecimen is removed from the beaker, rinsed in naphtha, dried andweighed. Acidity in terms of KOH per gram of oil product is alsodetermined.

The loss in weight of the test specimen is recorded after each Weighing.

This test, known as the Sand Stirring Corrosion Test, is referred tohereinafter as SSCT.

The following products were subjected to the above test and resultstabulated in Table II.

Product A--(Control) Solvent-extracted 30 SAE base oil +33%barium-containing neutralized reaction product of P 8 and a polybuteneof about 1000 molecular weight.

Product B-A+1.5% product of Example IV.

Product C--A+1.5% product of Example VI.

Product D-A+1.0% product of Example VI.

Product E--A+0.75% product of Example VI.

Table II Acidity (mg. KOH/g. Corrosion (mg.

oil) wt. loss) Product Hours Housr Hours Hours Hours A (Control) 6.1614.0 16. 8 698 1, 360 B 1.4 2. 8 5.0 114 201 G 1. 4 2.8 3. 6 52 81 10 D.1.12 2.8 5.08 101 154 E 0. 84 4. 2 7. 28 132 265 Since weight losses of200 milligrams in 48 hours and 500 milligrams in, 72 hours are permittedin the test, the corrosion inhibiting properties of the herein describedphosphorus sulfide derivatives is clearly demonstrated by the abovedata.

While this invention has been described in connection with the use ofthe herein described additives and lubricant compositions, their use isnot limited thereto but the same can be used in products other thanlubricating oils, such as for example, fuel oils, insulating oils,greases, non-drying animal and vegetable oils, waxes, and asphalts.

Concentrates of a suitable oil base containing more than 10%, e.g. fromabout to about 50% or more, of the herein described derivatives, alone,or in combination with more than 10% of other additives, can be used forblending with other oils in proportions desired for the particularcondition or use to give a finished product containing from about 0.05%to about 10% of the described derivative.

Lubricant composition containing the herein described derivatives cancontain other addition agents such as, for example, antioxidants, pourpoint depressors, V.I. improvers, etc.

Unless otherwise stated, percentages given herein and in the appendedclaims are weight percentages.

Although the present invention has been described with reference tospecific preferred embodiments thereof, the invention is not to beconsidered as limited thereto, but includes within its scope suchmodifications and variations as come within the spirit of the appendedclaims.

I claim:

1. A lubricant composition comprising a major proportion of anoleaginous material and from about 0.05 to about 10% of a phosphorusandsulfurcontaining reaction product of a phosphorus sulfide and an adductof hexachlorocyclopentadiene with a polyolefin having from about 4 toabout 60 carbon atoms and 2 to about 3 double bonds, said reactionproduct being obtained by reacting said adduct with from about 2% toabout 50% of a phosphorus sulfide at a temperature of from about 85 C.to about 200 C. for a time suflicient to complete said reaction, andrecovering the resultant reaction product.

2. A lubricant composition as described in which the polyolefin isbutadiene.

3. A lubricant composition as described in which the polyolefin isisoprene.

4. A lubricant composition as described in which the polyolefin isl-vinylcyclohexene.

5. A lubricant composition as described in which the polyolefin isdl-limonene.

6. A lubricant composition as described in which the polyolefin ismyrcene.

7. A lubricant composition as described in claim 1 in which thephosphorus sulfide is phosphorus pentasulfide.

8. A lubricant composition comprising a major amount of a hydrocarbonlubricating oil, from about 0.05% to about 10% of a phosphorusandsulfur-containing reaction product of a phosphorus sulfide and an adductof hexachlorocyclopentadiene with a polyolefin having from about 4 toabout carbon atoms and 2 to about 3 double bonds, said reaction productbeing obtained by reacting said adduct with from about 2% to about 50%of a phosphorus sulfide at a temperature of from about C. to about 200C. for a time sufiicient to complete said reaction, and recovering theresultant reaction product.

9. A lubricant composition as described in claim 8 in which thepolyolefin is butadiene.

10. A lubricant composition as described in claim 8 in which thepolyolefin is isoprene.

11. A lubricant composition as described in claim 8 in which thepolyolefin is l-vinylcyclohexene.

12. A lubricant composition as described in claim 8 in which thepolyolefin is dl-limoneue.

13. A lubricant composition as described in claim 8 in which thepolyolefin is myrcene.

14. An addition agent concentrate for lubricating oils consistingessentially of a lubricating oil containing more than 10% and up toabout 50% of a phosphorusand sulfur-containing reaction product of aphosphorus sulfide and an adduct of hexachlorocyclopentadiene with apolyolefin having from about 4 to about 60 carbon atoms and 2 to about 3double bonds, said reaction product being obtained by reacting saidadduct with from about 2% to about 50% of a phosphorus sulfide at atemperature of from about 85 C. to about 200 C. for a time sufficient tocomplete said reaction, and recovering the resultant reaction product,said concentrate being capable of dilution with a lubricating oil toform a homogeneous mixture containing from about 0.05% to about 10% ofsaid reaction product of said phosphorus sulfide and said adduct ofhexachlorocyclopentadiene with said polyolefin.

in claim 1 in claim 1 in claim 1 in claim 1 in claim 1 References Citedin the file of this patent UNITED STATES PATENTS 2,881,196 Fields Apr.7, 1959 2,900,377 Fields Aug. 18, 1959

1. A LUBRICANT COMPOSITION COMPRISING A MAJOR PROPORTION OF AN OLEAGINOUS MATERIAL AND FROM ABOUT 0.05% TO ABOUT 10% OF A PHOSPHORUS-AND SULFUR-CONTAINING REACTION PRODUCT OF A PHOSPHHORUS SULFIDE AND AN ADDUCT OF HEXACHLOROCYCLOPENTADIENE WITH A POLYOLEFIN HAVING FROM ABOUT 4 TO ABOUT 60 CARBON ATOMS AND 2 TO ABOUT 3 DOUBLE BONDS, SAID REACTION PRODUCT BEING OBTAINED BY REACTING SAID ADDUCT WITH FROM ABOUT 2% TO ABOUT 50% OF A PHOSPHORUS SULFIDE AT A TEMPERATURE OF FROM ABOUT 85*C. TO ABOUT 200*C. FOR A TIME SUFFICIENT TO COMPLETE SAID REACTION, AND RECOVERING THE RESULTANT REACTION PRODUCT. 